The present invention relates to novel processes to produce oil well drilling, completion and hydrofracturing fluids, that comprise industrial streams comprising glycerin, preferably produced when processing triglycerides. Triglyceride containing feedstocks, such as vegetable and animal oils and fats, have been employed traditionally to produce soaps and other materials, such as fatty acids with crude glycerin streams as by-products of these processes. Virtually all of this crude glycerin was refined and distilled to produce purer grades, such as USP, technical grade and food grades, such as kosher or halal. Until recently there was a substantial market for pure glycerin, beyond that generated by processing of fats and oils. For example, Dow operated a plant in Freeport Tex. producing 60,000 tons/yr. of synthetic glycerin based on hydrocarbon feedstocks.
From a small start in the early 1990s, to a larger industry today, triglyceride-containing feedstocks have been reacted with alcohols to produce monoesters that are used as diesel fuel—“biodiesel”. In 2011 biodiesel production in the United States reached one billion gallons. As 0.7 pounds of glycerin is produced for each gallon of biodiesel, Glycerin production from this source amounted to about 350,000 tons of glycerin. In the face of this production Dow has shut down the Freeport facility, and finding stable, profitable markets for this product has been an important factor in the economics of biodiesel production.
The processes of this invention provide a means to meet this long felt need by employing the crude glycerin by-products of triglyceride processing in production of products for use in producing oil and gas well fluids. Glycols are also a useful component of certain glycerin-based drilling and completion fluids. Propylene glycol recovered from industrial applications, such as aircraft deicing operations, can be an economic source of this material.
Oil and Gas Well Fluids—Drilling Fluids and Completion Fluids
Drilling fluids, generally referred to as muds, are employed in drilling oil and gas wells to perform several functions. These were summarized by the Institute of Petroleum in “Modern Petroleum Technology”, as follows;                a. to remove cuttings continuously at reasonable velocities while ensuring that they need not be ground too finely before being lifted to the surface;        b. to release the cuttings and the detritus readily from the return mud on screens and in settling pits;        c. to form a gel, when flow ceases, so that cuttings entrained in the mud column do not settle down in the bottom of the hole;        d. to act as a lubricant and coolant for the bit and drill column;        e. to maintain the requisite pressures in the bore hole in excess of the reservoir pressures existing in gas, oil and water bearing reservoir fluids.        
Once the drilling operations are completed, “completion” fluids are needed to contain the formation pressure during completion and servicing (workover) operations. Muds employed in drilling are occasionally used for this purpose, but more often, “clear” liquids including brines, such as solutions of zinc or calcium chlorides or bromides, are used to create a density adequate to contain the reservoir pressure during completion and workover operations. In practice, densities can range from about 8.4 to over 20 pounds per gallon.
Drilling fluids fall into two general categories; water-based muds and oil-based muds. Employing water-based mud when drilling through shale formations has led to several problems including sloughing shale, tight hole, gradual hole enlargement, poor hole cleaning, high torque and cementing failures (Ismail, I & Huang, A. P., Journal Technologi, 50(F) 53-65© University Technologi Malaysia). While oil-based mud addresses these issues, its use has become restricted due to environmental regulations. In response to this situation, a number of developers have identified compounds that can be added to water-based drilling and completion fluids in order to mitigate the effects of water on shale formations.
Peterson (U.S. Pat. No. 4,780,220) teaches the use of glycerine and polyglycerine in drilling and completion fluids for use in shale formations, as well as the use of glycols to control the foaming tendency of glycerine in these applications. Peterson further teaches that the concentration of glycerine should be at least 6%, but preferably more than 25% in order to inhibit shale swelling.
Walker (U.S. Pat. No. 5,403,820) teaches the use of alkyl glucosides—particularly methyl glycoside—in a water-based drilling fluid to inhibit shale swelling. He also teaches that it is preferred that the drilling fluid in this instance also contain at least 2% of an alkali metal hydroxide in order to have a pH above 8.5, and preferably 9-12.
In addition to the above enumerated constituents, drilling and/or completion fluids typically contain other additives including corrosion inhibitors, weighting agents (including salts, barites and other clays), defoamers, emulsifiers and biocides.
Schilling et al (U.S. Pat. No. 6,806,231) teaches advantages to employing beet molasses together with methyl glucoside, and that a salt—NaCl or KCl—appears to assist the shale-swelling effects of methyl glucoside. Schilling also identifies maltodextrins, carboxymethyl starches and hemicelluloses as useful constituents of drilling fluids.
Special mention is made of Sapienza, et al (U.S. Pat. No. 7,138,071) that teaches the inclusion of a variety of components as freezing point depressants in drilling fluids; including alkyl aldosides, maltodextrins and glycols and/or glycerin recovered from aircraft deicing operations. Also, to be noted, Sapienza, et al (U.S. Pat. No. 6,890,451) teaches inclusion of glycerin and glycerin-containing by-products of triglyceride processing as freezing point depressants in oil and gas well drilling fluids.
Taking the existing background into consideration, a need exists for economic sources of the ingredients of environmentally benign water-based drilling and completion fluids for application to oil and gas wells.
Oil & Gas Well Fluids—Hydraulic Fracturing Fluids
At this time, in response to the growing need for clean energy sources, there exists a dramatic expansion in drilling operations associated with development of natural gas and hydrocarbon liquid resources associated with deep shale formations. This resource has now become economically viable through the development of advanced directional drilling techniques that permit drilling in several lateral directions from a given drilling site coupled with hydraulic fracturing (hydrofracturing) techniques that enable production of hydrocarbons from tight shale formations.
In addition to drilling and completion fluids, the above mentioned hydrofracturing techniques employed in production of hydrocarbons from tight shale formations employ substantial quantities of a fluid comprising primarily water and a “propping” agent, such as sand. This fluid is introduced at high pressure into the completed well to initiate and expand fractures in the shale formation thereby enabling an economic rate of recovery of hydrocarbons. These fluids also contain a small percentage (ca 0.5%) of “chemicals” (a chemicals package) that provide useful properties to the hydrofracturing fluid.
(D. Arthur, et al—Hydraulic Fracturing Considerations for Natural Gas Wells of the Marcellus Shale) presents a discussion of hydrofracturing with particular reference to the Marcellus shale of the Appalachian region. They state; “The fluids currently being used for fracture treatments in the Marcellus shale are water based or mixed slickwater fracturing fluids. Slickwater fracturing fluids are water-based fluids mixed with friction-reducing additives, primarily potassium chloride.” The amount of hydrofracturing fluid used in a typical well can range from 2 to 4 million gallons.
“Modern Shale Gas Development in the United States—a Primer”, a US DOE publication, presents the following breakdown of the “chemicals package” in percentages as contained in a typical hydrofracturing fluid;
Componentvol %acid0.123friction reducer0.088surfactant0.085KCl0.06gelling agent0.056scale inhibitor0.043pH adjusting agent0.011breaker0.01crosslinker0.007iron control0.004corrosion inhibitor0.002biocide0.001total0.490
The additives depicted in the above Table represent less than 0.5% of the total fluid volume. Overall the concentration of additives in most slickwater fracturing fluids is a relatively consistent 0.5% to 2% with water making up 98% to 99.5%.
Exhibit 35 of this DOE publication presents specific compounds that are used to provide the functions enumerated above. One of the concerns surrounding these hydrofracturing operations is the potential for contamination of potable water sources should the chemical-containing hydrofracturing water enter any natural aquifers in the area.
These developments are leading to an increasing need for economic sources of environmentally benign components of the chemical package added to hydrofracturing water.
Materials Employed in the Processes of this Invention
The present inventor has found that the issues and markets discussed above can be addressed by processes utilizing certain by-products and waste streams as described below.
The biodiesel industry, driven by US and European statutory requirements for alternative fuels, has led to a substantial increase in the supply of by-product crude glycerin and to a decrease from the historic price of both crude and refined glycerin from all sources. Against this background, the present invention provides novel methods for producing desirable products for use as oil and gas well drilling, completion and hydrofracturing fluids, while at the same time reducing the costs of producing glycerin-containing products employing purer grades of glycerin.
The principal by-products for use in the present invention comprise the glycerin produced during several processes that employ raw materials comprising triglycerides. These raw materials include vegetable and animal oils and fats including, without limitation, soy and rapeseed oils and waste cooking oils.
Production of Monoesters, Soap and Fatty Acids
Triglyceride-containing raw materials are processed by several processes including;                1. Transesterification reactions with monoalcohols to produce monoesters. Production of monoesters has grown in response to the need for alternative fuels as monoesters, known as “biodiesel,” which can function as an alternative or supplement to the use of petroleum-derived diesel fuel.        2. Hydrolysis of triglycerides to produce fatty acids for sale as such or for subsequent reaction with monoalcohols to produce monoesters, or with alkalis to produce soap.        3. Saponification (reaction with alkalis) to produce soap.        
All of these reactions produce glycerin-containing by-product streams of varying purity. These processes are described more fully below.
a) Transesterification Crude Glycerin
This process is typically catalyzed by a homogeneous catalyst system employing as a catalyst either a base or an acid. The base catalyzed route is the most popular because of reaction efficiency, mild operating conditions and as it requires only simple materials of construction. Typically, the base catalyst will be NaOH or KOH dissolved in the alcohol that will be employed as a reactant in the process. Methanol is typically employed, but higher alcohols may be used.
The principal products of the transesterification reaction, oil-soluble monoesters and water-soluble glycerin—are typically separated by gravity decanting. The monoester phase is generally water-washed to remove any remaining glycerin, alkaline catalyst, soaps formed during the reaction and other water soluble impurities. This wash water is normally added to the glycerin phase to constitute a by-product glycerin stream. The resulting glycerin-containing stream (with or without the addition of wash water) is termed “transesterification crude glycerin,” for convenience in the present specification. Both the monoester and the glycerin by-product will normally contain unreacted alcohol that typically are be removed by stripping and recycled to the reactor or disposed of otherwise.
Transesterification crude glycerin is often neutralized with an acid to convert the remaining alkaline catalyst to a salt and to convert soaps formed in the transesterification reaction to free fatty acids. Formation of soap during the transesterification reaction can result from the presence of free fatty acids in the triglyceride-containing raw material or from water in any of the materials being processed.
The fatty acids resulting from the reaction of the acid with any soaps formed can be recovered by gravity or centrifuge assisted separation. The remaining glycerin phase is termed “neutralized transesterification crude glycerin” and will generally comprise water, glycerol, the salt of the base catalyst and, depending on the efficiency of the separation of free fatty acids and other organic materials, MONG (matter organic not glycerol). A typical analysis of neutralized transesterification crude glycerin is shown in Table 1.
TABLE 1Componentwt %Glycerin86.4salt3.1water10.5MONGneg.
There is considerable flexibility in choice of the base employed as a catalyst and in the acid used for neutralization. Consequently the crude glycerin could comprise one of several bases such as NaOH and KOH, while the salts contained in the neutralized stream could be sodium or, potassium salts such as acetates, chlorides, sulfates, lactates, etc.
b) Heterogeneous Catalyzed Transesterification Crude Glycerin
As taught by Stern (U.S. Pat. No. 5,908,946), a transesterification reaction employing a solid catalyst comprising zinc and alumina, with carefully controlled conditions can produce esters and a relatively pure glycerin by-product. At the same time minor impurities may be present in the glycerin by-product depending on the purity of the triglyceride raw material. For example, unless the raw materials (oils, fats and alcohol) are essentially water free, soaps may be formed that would be included in this crude glycerin. For purposes of this discussion this glycerin-containing stream will be referred to as “heterogeneous catalyzed transesterification crude glycerin.”
In both the homogeneous and heterogeneous catalyst cases, water and or free fatty acids in the feed can react to form soaps that in turn will become free fatty acids following acidification of the crude glycerin. If a purer glycerin is desired, care is taken to avoid water and free fatty acids in the feeds can be esterified with glycerin to triglycerides before entering the transesterification reactor.
c) Hydrolysis Crude Glycerin
Hydrolysis of triglyceride-containing vegetable and animal fats and oils typically takes place at high temperature and pressure (ca 500 F and 600 psi) in a vertical counter-flow reactor with the fat/oil phase flowing upward and the hot water phase flowing downward. Reactor overheads contain the fatty acid product and the bottoms stream (hydrolysis crude glycerin) is a water/glycerol stream containing about 12-25% glycerol with a small amount of impurities, such as dissolved fatty material and proteins. The fatty acids produced can be reacted with caustic to produce soaps or with alcohols to produce monoesters that may be employed as biodiesel.
d) Saponification Crude Glycerin
Saponification, an alkaline hydrolysis of fats and oils with caustic, is the traditional method for manufacture of soap. In this method, fats and/or oils are mixed with caustic (such as sodium hydroxide) and boiled. After cooling, salt (NaCl) is added causing the mixture to separate into two layers with the “neat” soap on top and “spent lye” on the bottom. The “spent lye” is the primary by-product and comprises a mixture of glycerol, salt and unreacted caustic together with small quantities of unseparated soap. Typically this spent lye will contain 5-15% glycerol and 8-20% salt. Processing of the spent lye to recover glycerol can proceed through the following steps:                a. Skimming off most or all of the free soap and then boiling the spent lye with fatty acid to remove free caustic followed by cooling and further skimming.        b. Removal of impurities by coagulation with alum or ferric chloride (purified spent lye).        c. Neutralization with an acid, such as HCl (neutralized spent lye).        d. Addition of caustic to raise the pH range to 8.5-9.0 (pH adjusted spent lye).        
In the present invention, the glycerol-salt solution obtained at any point in the above sequence (“saponification crude glycerin”) could be employed as a raw material for the processes of this invention.
Distillation of Glycerin
Distillation is traditionally employed to produce essentially pure glycerin products (e.g. USP, technical grade, kosher, etc) from the crude glycerins described above. The Crown Iron Works website brochure describes distillation of crude glycerin from biodiesel production.
As the atmospheric boiling point of glycerin is 290° C., these distillation processes are normally conducted under vacuum to avoid high temperatures that would degrade the glycerin product. In the case of the crude glycerin from hydrolysis, the 12-25% crude glycerin can be processed without a vacuum through multi-stage evaporation to a concentration of about 88% prior to being distilled under vacuum in the manner described above. The Lurgi website brochure illustrates processing of hydrolysis glycerin that has been concentrated in this manner.
As an alternative to vacuum distillation, it is also possible to employ steam distillation employing systems known to persons skilled in the art, such as vapor recompression, as a means of avoiding excessive temperatures.
Crown Iron Works reports that bottoms from the still will contain 65-75% glycerin. If a neutralized transesterification crude glycerin as shown in Table 1 were being processed, this level of recovery would lead to rejection in the bottoms product of about 7-10% of the glycerin contained in the crude glycerin being processed. As the principal objective in these distillation processes is to maximize recovery of glycerin as a pure product, the vendors suggest that the bottoms product from the still—comprising some glycerin together with the salt and MONG contained in the crude glycerin—be processed in either a “foots” still or a thin film evaporator in order to maximize recovery of glycerin in a pure form.
Bottoms from these operations have been typically marketed as livestock feed additives or disposed of as wastes.
Membrane Separation Techniques
Muraldihara, in International Application WO 2008/156612, describes the application of membrane separation techniques to purification of crude glycerin. Membranes are designed to separate on the basis of molecular size. In descending order of molecule size, they can be ranked as follows;                microfiltration—300-20,000 Å        ultrafiltration—25-1500 Å        nanofiltration—9-70 Å        reverse osmosis—1-20 Å        
In the processes of this invention, membrane separation may be employed to remove organic materials (MONG). Muraldihara shown a case in which a 32.9% glycerol, 2% NaCl and 1.0% MONG solution in water was processed through a nanofiltration membrane (MPS34 produced by Koch) yielding 89.6% of a stream containing 33.03% glycerol, 1.71% NaCl with no remaining MONG.
When processing glycerin streams containing low concentrations of water to remove MONG, it is preferable to add water for membrane separation to reduce the pressure needed to effect the separation. This need not be an issue in the present case as the oil and gas fluids being produced will require water in any event.
Recovery of Glycol from Industrial Waste Streams
In addition to glycerin-containing products, in certain cases the present invention also may make use of glycol recovered from industrial waste streams.
Airports, in response to environmental concerns, are increasingly turning to collection and processing of the waste dilute streams of propylene glycol resulting from aircraft deicing applications (Stormwater—March-April 2008—“Aircraft Deicing Fluid—The Recycling Solution”). Also, propylene glycol can be recovered from waste heat transfer fluids and gas dehydration fluids.
Inland Technologies, Inc, in its website brochure, describes a concentrator that will produce a 50-60% glycol solution from deicing wastes containing 1-20% glycol. The concentrated product would be a useful additive to glycerin-containing drilling and completion fluids to avoid foaming. Other firms are offering similar products including the use of membrane separations.
Thus, there also exists a need in the art for processes by which glycol in industrial waste streams can be used economically and efficiently.